A new silver cluster that emits bright-blue phosphorescence

Article abstract of DOI:10.1039/c9cc09439c

A new hexanuclear silver(i) cluster (NC-Ag6) that emits bright-blue phosphoresce with a lifetime of 22.4 μs and a quantum yield (QY) of 22% under ambient conditions was synthesized. A film combining NC-Ag6 with yellow cerium(iii)-doped yttrium aluminum garnet phosphors (YAG:Ce³⁺) displays chameleon -like emission (including white), which is related to excitation-dependent F?rster resonance energy transfer (FRET) between dual phosphors. The mechanoresponsive luminescence colour of this silver cluster ranges from blue to green virtually without loss of QY.

Full text of DOI:10.1039/c9cc09439c

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Yang, M. Zhang,
Z. Han, H. Li, L. Li, X. Dong, S. Zang and T. C. W. Mak, Chem. Commun., 2020, DOI:
10.1039/C9CC09439C.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC09439C
ChemComm
COMMUNICATION
A new silver cluster emitting brightly blue phosphorescence†
Jin-Sen Yang,a Miao-Miao Zhang,a Zhen Han,a Hai-Yang Li,a Lin-Ke Li,a Xi-Yan Dong,*a,b Shuang-
Quan Zang,*a and Thomas C. W. Makc
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A new hexanuclear silver (I) cluster (NC-Ag6) emits brightly blue
phosphoresce with a lifetime of 22.4 μs and quantum yield (QY) of
22% under ambient conditions was synthesized. The film
combined NC-Ag6 with yellow cerium (III)-doped yttrium
aluminum garnet phosphors (YAG : Ce3+) displays chameleon-like
emission, including white color, which is related to excitation-
dependent Förster resonance energy transfer (FRET) between
dual phosphors. The mechanoresponsive luminescence color of
this silver cluster ranged from blue to green nearly without the
loss of QY.
improve luminescence intensity and quantum yield, which can
be achieved by choosing suitable ligands.15
At present, the limitation of organic light emitting diodes
(OLEDs) were efficient blue phosphorescent emitters16
because the preparation of blue phosphors is far more difficult
than green, orange and red ones.16b Most of the well-known
blue phosphorescent emitters are based on heavy transition
metal including iridium (Ir), platinum (Pt), and gold (Au), while
silver clusters showing blue phosphorescence at RT are rare.16,
17
In this work, we have used a tridentate diphosphate
pyridine ligand, 2,6-bis-diphenylphosphanyl-pyridine (dpppy),
which has not only electron-donating P atoms, but also
electron-accepting aromatic rings, including pyridine and
benzene rings. The reaction of silver trifluoroacetate
(CF3COOAg) and dpppy ligand afforded a hexanuclear silver (I)
cluster Ag6(dpppy)2(CF3COO)6 (NC-Ag6). At room temperature,
NC-Ag6 displays strong blue phosphorescence with a lifetime
of 22.4 μs and quantum yield up to 22%. NC-Ag6
demonstrated high thermostability over 100 °C in air. The film
incorporating blue NC-Ag6 and yellow cerium (III)-doped
yttrium aluminium garnet (YAG : Ce3+) phosphor shows
excitation-dependent emission color, including white emission.
In addition, the silver cluster shows interesting
mechanoresponsive luminescence colour from blue to green
with negligible loss of QY.
Single-crystal X-ray diffraction (SCXRD) analysis reveals that
NC-Ag6 belongs to monoclinic space group P21/n. An
asymmetric unit of this structure contains three Ag(I) ions, one
dpppy ligand and three CF3COO- (Figure 1a). P and N atoms of
dpppy are connected with silver ions in the monodentate
mode (Figure 1b), and the CF3COO- coordinate to silver ions in
three modes of μ3-κ2: κ1; μ2-κ1: κ1 and μ2-κ2: κ0 (Figure 1c, S1).
Atomically precise metal nanoclusters as a link between
discrete metal atoms and metal nanocrystalline have garnered
significant attention.1 The well-defined structure as well as
distinctive physical and chemical properties such as
luminescence,2, 3 chirality and catalysis, made these materials
5
to be explored widely.4, Silver clusters have also gained
increasing interest due to many unusual properties,6 especially
luminescence.7 Enormous studies have shown that silver
cluster is a potential room temperature (RT) phosphorescent
material.8 However, the inherent instability and poor room-
temperature photoluminescence quantum yield (QY) are
unresolved problems.9 Meanwhile, deficient luminous gamut
especially blue light severely depressed their practical
application. Researchers have developed various strategies to
improve luminescence performance, such as alloying,10
11
aggregation-induced emission (AIE),4a,
rigidification by
surface shell engineering,12 building cluster-based networks8b,
and constructing a new path of luminescence.14
8c, 13
Combining published research results with our recent studies,
we find that introducing an effective charge transfer pathway
between metal and ligand is a very effective strategy to
Two adjacent Ag(I) clamped by four
argentophilic interactions (2.895 Å).
O atoms have
a. Green Catalysis Center, and College of Chemistry, Zhengzhou University, China. E-
mail: zangsqzg@zzu.edu.cn
The phase purity and formula of NC-Ag6 were further
verified by elemental analysis, powder X-ray diffraction (PXRD)
and electrospray ionization mass spectrometry (ESI MS)
(Figure.S2, S5). Most excitingly, NC-Ag6 has rarely high
thermal and photo-stability (Figure S2, S3).
b. College of Chemistry and Chemical Engineering, Henan Polytechnic University,
Jiaozuo 454000, China. E-mail: dongxiyan0720@hpu.edu.cn
c. Department of Chemistry, The Chinese University of Hong Kong, Shatin, New
Territories, Hong Kong SAR. China.
† Electronic Supplementary Information (ESI) available. CCDC 1966339. For ESI and
crystallographic data in CIF or other electronic format see DOI:10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
temperature was at 420 nm with decay of 0.75 ns, and
View Article Online
DOI: 10.1039/C9CC09439C
dpppy’s quantum yield was 4% which was lesser than that of
NC-Ag6 (22.4%).
Density functional theory (DFT) calculation was conducted
to understand the origins of the emissions from NC-Ag6 and
dpppy. The DFT results show that dpppy’s LUMO–LUMO+5
(LUMO: the lowest degenerate unoccupied molecular orbital)
are localized on the pyridyl group (–Py), (Figure S9, Table S3).
In contrast with NC-Ag6 LUMO–LUMO+3 is centred on –Py of
dpppy ligand, while LUMO+4–LUMO+5 is distributed on the
diphenylphosphinyl group (–PPh2) of dpppy ligand. (Figure S11,
Table. S4). It is suggested that an inversion of unoccupied
molecular orbitals before and after dpppy coordinate with
silver ions at higher energy levels. Absorption transition
analysis from time-dependent density functional theory (TD-
DFT) calculations reveals the absorption of dpppy at 304nm
mainly originating from the transition of HOMO → LUMO and
the absorption at 271nm mainly originating from the HOMO-1
→ LUMO+1 (Figure S10). For NC-Ag6, the absorption at 295
nm mainly originating from HOMO → LUMO+5 and the
absorption at 279 nm that mainly originating from HOMO-4 →
LUMO+3 and HOMO-5 → LUMO+2 (Figure S12). Further, the
spin−orbit coupling (SOC) matrix of NC-Ag6 between the
lowest singlet excited states and triplet excited states were
calculated by the ORCA program with B3LYP/def2SVP by an
atomic mean-field spin–orbit approach. The SOC values were
determined to be 1.83 and 0.46 cm−1 of S1 → T1 and S2 → T1,
while 0.51 and 1.76 cm−1 of S1 → T2 and S2 → T2 for higher-
level transitions, suggesting that the phosphorescence decay
would primarily be related to S1 → T1 or S2 → T2 states.
Combining theoretical calculation and experimental
luminescent properties, we speculate that the RT
phosphorescence emission could arise from a new interligand
trans-metallic charge-transfer transitions (ITCT, O/Ag →dpppy)
that are formed by the ligand coordinate with silver ions.8b
Figure 1 (a) The molecular structure of NC-Ag6. The coordination modes of dpppy (b)
and CF3COO- (c) with Ag atoms. Color code: Ag, green; F, cyan; C, gray; N, blue; P,
purple; O, red. All hydrogen atoms were omitted for clarity.
NC-Ag6 emits intense blue light excited by 365 nm at room
temperature (Figure S6), and the maximum emission remains
at 453 nm (Figure 2a). The UV-vis absorption spectrum in
dichloromethane shows two absorption peaks at 250 and 280
nm, which corresponds to the excitation spectrum (Figure 2a,
S7). The luminescence lifetime is 22.4 μs with an RT QY of 22.4%
(Figure 2e, Table S1), suggesting that the emission could be
spin-forbidden phosphorescence, which is independent on
excitation (Figure 2b). Temperature-variable luminescence
measurements reveal that the luminescence intensity and
lifetime decreases initially and then increases (Figure 2c, S8,
Table S2). The emission properties of dpppy ligand were also
examined to compare the luminescent properties of dpppy
and NC-Ag6 (Figure 2a, 2d, Table S1). The emission peak of the
free ligand at room
Subsequently,
a white light-emitting (WLE) film was
fabricated by combining NC-Ag6 and YAG : Ce3+ with
polymethyl methacrylate and were excited by 370 nm UV light
(Supporting information). The CIE chromaticity diagram (0.33,
0.36) of the film is very close to pure white light (0.33, 0.33)
(Figure 3b, 3d) and the QY of WLE film is measured to be 15%,
which endows the luminescent film suitable for WLED. The
emission spectrum of WLE film displays two major emission
bands at 430nm and 512nm, originating from NC-Ag6 and
YAG : Ce3+ respectively (Figure 3a). The emission lifetime of
WLE film at 512 nm was determined to be 14.79 μs and the
luminescence of YAG : Ce3+ component film at 540 nm was
63.94 ns (Figure S14). Meanwhile, the electronic spectrum of
YAG : Ce3+ and the emission spectrum of NC-Ag6 showed good
overlap (Figure S13). Therefore, we postulate that there could
be a förster resonance energy transfer (FRET)18 between two
components. The energy transfer efficiency (E) was 9% which
was calculated according methods reported before.18c In
addition, the fabricated film has excitation dependent
emission (Figure 3d), which could be applied in the field of
anti-counterfeiting.
Figure 2 (a) Normalized excitation (Ex : dotted lines) and emission (Em : solid lines)
spectra of NC-Ag6 (blue) and dpppy (purple) at room temperature. (b) Normalized
emission spectra of NC-Ag6 at the different excitation wavelengths. (c) Temperature-
dependent emission spectra of NC-Ag6 excited at 365 nm. RT time-resolved emission
decays spectrum of the free ligand dpppy at 420 nm excited at 330 nm (d) and the
silver cluster NC-Ag6 at 453 nm excited at 355 nm (e).
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
View Article Online
DOI: 10.1039/C9CC09439C
Figure 4 (a) Photos of the ground (right) and intact (left) crystalline powder of NC-Ag6.
(b) PXRD recorded at room temperature of NC-Ag6 before and after grinding and
treated with DCM. (c) Normalized excitation (Ex : dotted lines) and emission (Em : solid
lines) spectra of NC-Ag6 before (purple) and after grinding (green) and treated with
DCM (blue) at room temperature.
Figure 3 (a) Normalized excitation (Ex : dotted lines) and emission (Em : solid lines)
spectra of NC-Ag6 (blue) and YAG : Ce3+ (yellow) at room temperature. (b) Emission
spectrum of WLE film excited at 370 nm, the insert shows the process of FRET between
NC-Ag6 and YAG : Ce3+ and photos of the WLE film irradiated with visible light (left)
and 365 nm UV lamp (right), respectively. (c) Normalized emission spectra of WLE film
at different excitation wavelengths (d) CIE coordinates of WLE film at different
excitation wavelengths, the red dot is CIE coordinates excited at 370 nm.
show that the absorption increased at 256 nm with the
grinding process (Figure. S7), and solid diffuse reflectance
spectra also show absorption enhancement at 475 nm (Figure.
S20). These changes could be attributed to more serious π–π
stacking that caused by disorder molecular arrangement after
grinding.21
In conclusion, we have synthesized a new hexanuclear silver
cluster with high quantum yield and microsecond emission
lifetime. According to the favourable luminescence properties
of the NC-Ag6, WLE film fabricated by the cluster and YAG :
Ce3+, which is expected to be applied to lighting devices.
Interestingly, the silver cluster shows mechanoresponsive
luminescence. When the solid sample (NC-Ag6) is ground
strongly in an agate mortar, the luminescence colour changes
from the initial blue to green (Figure 4a). The photoemission
curves in figure 4c shows that the NC-Ag6 emission centre was
at 453nm before grinding and after grinding the emission
centre shifted to 493 nm with a 40 nm red-shift. After the
grinding of NC-Ag6, a negligible loss of QY (Table S5) was
observed. PXRD was conducted to track the effect of the
grinding process on the crystal structure (Figure 4b). The
results show that the sample diffraction is obviously
broadened when treated with grinding, which is a common
change from the crystal phase to the amorphous phase.19
Although the diffraction peak broadened, there is no new
crystal plane formed. Scanning electron microscopy recorded
the change of morphologic before and after grinding (Figure
S17), which shows the grinding process makes the cluster
from regular strips changes to amorphous aggregate. The
changes of crystalline phase and emission properties caused
by grinding can be recovered by drop tiny amounts of
dichloromethane (DCM) to crushed sample (Figure 4b, 4c).
The results indicate that the grinding process is accompanied
by the changes of crystal packing structure, which was often
Additionally,
interesting
recyclable
mechanochromic
luminescence was also revealed.
Conflicts of interest
There are no conflicts to declare.
Acknowledgments
This work was supported by the National Science Fund for
Distinguished Young Scholars (no. 21825106), the National
Natural Science Foundation of China (no. 21671175,
21975065), the Program for Science & Technology Innovation
Talents in Universities of Henan Province (164100510005), the
Program for Innovative Research Team (in Science and
Technology) in Universities of Henan Province (19IRTSTHN022)
used
to
explain
mechanoresponsive
luminescence and Zhengzhou University.
properties.19, 20 Fourier transform infrared (FT-IR) spectra and
1H nuclear magnetic resonance (NMR) spectra give the same
value corresponding to before and after grinding, that
indicates that the change in phosphorescence colour is caused
by physical processes rather than chemical reactions (Figure.
S18, S19). Figure S21 shows the original crystalline sample has
weak π–π stacking between neighbouring aromatic rings
because of long distance (5.38 Å). UV-vis absorption spectra
Notes and references
1
(a) R. Jin, C. Zeng, M. Zhou and Y. Chen, Chem. Rev., 2016,
116, 10346−10413; (b) I. Chakraborty and T. Pradeep, Chem.
Rev., 2017, 117, 8208−8271;.(c) X. Kang and M. Zhu, Chem.
Soc. Rev., 2019, 48, 2422−2457; (d) Z. Lei, X. K. Wan, S. F.
Yuan, Z. J. Guan and Q. M. Wang, Acc. Chem. Res., 2018, 51,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
2465−2474; (e) Q. Yao, T. Chen, X. Yuan and J. Xie, Acc.
Chem. Res., 2018, 51, 1338−1348.
(a) A. Ghosh, R.-W. Huang, B. Alamer, E. Abou-Hamad, M. N.
Hedhili, O. F. Mohammed and O. M. Bakr, ACS Materials
Lett., 2019, 1, 297−302; (b) Z. Gan, J. Chen, J. Wang, C.
Wang, M. B. Li, C. Yao, S. Zhuang, A. Xu, L. Li and Z. Wu, Nat.
Commun., 2017, 8, 14739−14744.
Parida, M. N. Hedhili, O. F. Mohammed, O. M. Bakr, L.
View Article Online
Cavallo and J. M. Basset, Nanoscale, 2017, 9, 9529–9536.
11 (a) N. Goswami, Q. Yao, Z. Luo, J. LiD, OTI.: 1C0h.1e0n39a/Cn9dCJC.0X9i4e3,9CJ.
Phys. Chem. Lett., 2016, 7, 962–975; (b) S. Jin, W. Liu, D. Hu,
X. Zou, X. Kang, W. Du, S. Chen, S. Wei, S. Wang and M. Zhu,
Chem. Eur. J., 2018, 24, 3712–3715; (c) X. Kang, S. Wang and
M. Zhu, Chem. Sci., 2018, 9, 3062–3068.
2
3
(a) H. Yu, B. Rao, W. Jiang, S. Yang and M. Zhu, Coord. Chem.
Rev., 2019, 378, 595−617; (b) Z. Gan, Y. Lin, L. Luo, G. Han,
W. Liu, Z. Liu, C. Yao, L. Weng, L. Liao, J. Chen, X. Liu, Y. Luo,
C. Wang, S. Wei and Z. Wu, Angew. Chem. Int. Ed., 2016, 55,
11567−11571; (c) V. W. Yam, V. K. Au and S. Y. Leung, Chem.
Rev., 2015, 115, 7589−7728; (d) L. G. AbdulHalim, M. S.
Bootharaju, Q. Tang, S. Del Gobbo, R. G. AbdulHalim, M.
Eddaoudi, D. E. Jiang and O. M. Bakr, J. Am. Chem. Soc.,
2015, 137, 11970−11975; (e) Z. Lei and Q. M. Wang, Coord.
Chem. Rev., 2019, 378, 382−394.
(a) M.-M. Zhang, X.-Y. Dong, Z.-Y. Wang, H.-Y. Li, S. J. Li, X.
Zhao and S.-Q. Zang, Angew. Chem. Int. Ed., 2019, 58, 2−8;
(b) Y. Jin, S. Li, Z. Han, B.-J. Yan, H.-Y. Li, X.-Y. Dong and S.-Q.
Zang, Angew. Chem. Int. Ed., 2019, 58, 12143−12148; (c) S.
Li, X.-S. Du, B. Li, J.-Y. Wang, G.-P. Li, G.-G. Gao and S.-Q.
Zang, J. Am. Chem. Soc., 2018, 140, 594−597; (d) J. Yan, H.
Su, H. Yang, C. Hu, S. Malola, S. Lin, B. K. Teo, H. Hakkinen
and N. Zheng, J. Am. Chem. Soc., 2016, 138, 12751−12754;
(e) H. Yang, J. Yan, Y. Wang, G. Deng, H. Su, X. Zhao, C. Xu, B.
K. Teo and N. Zheng, J. Am. Chem. Soc., 2017, 139,
16113−16116.
(a) Y. Lei, F. Mehmood, S. Lee, J. Greeley, B. Lee, S. Seifert, R.
E. Winans, J. W. Elam, R. J. Meyer, P. C. Redfern, D.
Teschner, R. Schlögl, M. J. Pellin, L. A. Curtiss, S. Vajda,
Science, 2010, 328, 224−228; (b) M. Cao, R. Pang, Q.-Y.
Wang, Z. Han, Z.-Y. Wang, X.-Y. Dong, S.-F. Li, S.-Q. Zang and
T. C. W. Mak, J. Am. Chem. Soc. 2019, 141, 14505−14509; (c)
Z. Chang, X. Jing, C. He, X. Liu and C. Duan, ACS Catal., 2018,
8, 1384−1391.
(a) Y.-L. Li, Z.-Y. Wang, X.-H. Ma, P. Luo, C.-X. Du and S.-Q.
Zang, Nanoscale, 2019, 11, 5151−5157; (b) X. Y. Li, H. F. Su,
K. Yu, Y. Z. Tan, X. P. Wang, Y. Q. Zhao, D. Sun and L. S.
Zheng, Nanoscale, 2015, 7, 8284−8288; (c) Z. Wang, Y. M.
Sun, Q. P. Qu, Y. X. Liang, X. P. Wang, Q. Y. Liu, M. Kurmoo,
H. F. Su, C. H. Tung and D. Sun, Nanoscale, 2019, 11,
10927−10931; (d) X.-J. Xi, J.-S. Yang, J.-Y. Wang, X.-Y. Dong
and S.-Q. Zang, Nanoscale, 2018, 10, 21013−21018.
12 A. Nag, P. Chakraborty, M. Bodiuzzaman, T. Ahuja, S.
Antharjanam and T. Pradeep, Nanoscale, 2018, 10, 9851–
9855.
13 (a) M. J. Alhilaly, R.-W. Huang, R. Naphade, B. Alamer, M. N.
Hedhili, A. H. Emwas, P. Maity, J. Yin, A. Shkurenko, O. F.
Mohammed, M. Eddaoudi and O. M. Bakr, J. Am. Chem. Soc.,
2019, 141, 9585–9592; (b) Z.-Y. Wang, M.-Q. Wang, Y.-L. Li,
P. Luo, T.-T. Jia, R.-W. Huang, S.-Q. Zang and T. C. W. Mak, J.
Am. Chem. Soc., 2018, 140, 1069–1076; (c) J.-Y. Wang, R.-W.
Huang, Z. Wei, X.-J. Xi, X.-Y. Dong and S.-Q. Zang, Chem. Eur.
J., 2019, 25, 3376–3381.
14 (a) Z. Han, X.-Y. Dong, P. Luo, S. Li, Z.-Y. Wang, S.-Q. Zang &
T. C. W. Mak, Ultrastable atomically-precise chiral silver
clusters with over 95% quantum efficiency. Sci. Adv. 2019,
10.1126/sciadv.aay0107.
15 C. C. Hsu, C. C. Lin, P. T. Chou, C. H. Lai, C. W. Hsu, C. H. Lin
and Y. Chi, J. Am. Chem. Soc., 2012, 134, 7715–7724.
16 (a) X. Wang, Y.-L. Chang, J.-S. Lu, T. Zhang, Z.-H. Lu and S.
Wang, Adv. Funct. Mater., 2014, 24, 1911–1927; (b) Y. Chi
and P. -T. Chou. Chem. Soc. Rev., 2010, 39, 638–655.
17 (a) V. N. Kozhevnikov, Y. Zheng, M. Clough, H. A. Al-Attar, G.
C. Griffiths, K. Abdullah, S. Raisys, V. Jankus, M. R. Bryce and
A. P. Monkman, Chem. Mater., 2013, 25, 2352–2358; (b) A.
Szentkuti, M. Bachmann, J. A. Garg, O. Blacque and K.
Venkatesan, Chem. Eur. J., 2014, 20, 2585–2596; (c) C.-H.
Yang, M. Mauro, F. Polo, S. Watanabe, I. Muenster, R.
Fröhlich and L. De Cola, Chem. Mater. 2012, 24, 3684–3695;
(d) A. V. Artem’ev, M.Z. Shafikov, A. Schinabeck, O. V.
Antonova, A. S. Berezin, I. Y. Bagryanskaya, P. E. Plusnin and
H. Yersin. Inorg. Chem. Front., 2019, 6, 3168–3176.
18 (a) B. Dong, M. Tian, X. Kong, W. Song, Y. Lu and W. Lin,
Anal. Chem., 2019, 91, 11397–11402; (b) Y. Qin, L. J. Chen, Y.
Zhang, Y. X. Hu, W. L. Jiang, G. Q. Yin, H. Tan, X. Li, L. Xu and
H. B. Yang, Chem. Commun., 2019, 55, 11119–11122; (c) J. H.
Han, S. Park, F. H and H. Sugiyama, Chem. Eur. J. 2018, 24,
17091–17095.
4
5
6
7
19 Q. Benito, X. F. Le Goff, S. Maron, A. Fargues, A. Garcia, C.
Martineau, F. Taulelle, S. Kahlal, T. Gacoin, J. P. Boilot and S.
Perruchas, J. Am. Chem. Soc., 2014, 136, 11311–11320.
20 F. Ciardelli, G. Ruggeri and A. Pucci, Chem. Soc. Rev., 2013,
42, 857–870; (b) K. Nagura, S. Saito, H. Yusa, H. Yamawaki,
H. Fujihisa, H. Sato, Y. Shimoikeda and S. Yamaguchi, J. Am.
Chem. Soc., 2013, 135, 10322–10325; (c) Y. Sagara and T.
Kato, Angew. Chem. Int. Ed, 2011, 50, 9128–9132; (d) S. Xu,
R. Chen, C. Zheng and W. Huang, Adv. Mater., 2016, 28,
9920–9940.
(a) S. M. Swasey, S. M. Copp, H. C. Nicholson, A. Gorovits, P.
Bogdanov and E. G. Gwinn, Nanoscale, 2018, 10,
19701−19705; (b) V. W. Yam and K. M. Wong, Chem.
Commun., 2011, 47, 11579−11592; (c) J. Yang, N. Xia, X.
Wang, X. Liu, A. Xu, Z. Wu and Z. Luo, Nanoscale, 2015, 7,
18464−18470; (d) Z. Lei, X. L. Pei, Z. J. Guan and Q. M. Wang,
Angew. Chem. Int. Ed., 2017, 56, 7117−7120; (e) Z. Lei, X. L.
Pei, Z. G. Jiang and Q. M. Wang, Angew. Chem. Int. Ed.,
2014, 53, 12771−12775; (f) Q.-Q. Xu, X.-Y. Dong, R.-W.
Huang, B. Li, S.-Q. Zang and T. C. W. Mak, Nanoscale, 2015, 7, 21 (a) Z. Lu, W. Fan, S. Yang, X. Liu, Y. Qin, R. Zhao, L. Zheng and
1650–1654.
H. Z, Chem commun., 2019, 55, 8474−8477; (b) X. Cao, L.
Meng, Z. Li, Y. Mao, H. Lan, L. Chen, Y. Fan and T. Yi,
Langmuir., 2014, 30, 11753−11760.
8
9
(a) Z. Y. Chen, D. Y. S. Tam and T. C. W. Mak, Nanoscale,
2017, 9, 8930–8937; (b) R.-W. Huang, X.-Y. Dong, B.-J. Yan,
X.-S. Du, D.-H. Wei, S.-Q. Zang and T. C. W. Mak, Angew.
Chem. Int. Ed., 2018, 57, 8560–8566; (c) R.-W. Huang, Y.-S.
Wei, X.-Y. Dong, X.-H. Wu, C.-X. Du, S.-Q. Zang and T. C. W.
Mak, Nat. chem., 2017, 9, 689–697.
Ya. M. Su, H. Fe. Su, Z Wang, Y. A Li, S. Schein, Q. Q. Zhao, X.
Po. Wang, C. H. Tung, D Sun and L.S. Zheng, Chem. Eur. J.,
2018, 24, 15096–15103.
10 (a) G. Soldan, M. A. Aljuhani, M. S. Bootharaju, L. G.
AbdulHalim, M. R. Parida, A. H. Emwas, O. F. Mohammed
and O. M. Bakr, Angew. Chem. Int. Ed., 2016, 55, 5749–5753;
(b) M. S. Bootharaju, S. M. Kozlov, Z. Cao, M. Harb, M. R.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
View Article Online
DOI: 10.1039/C9CC09439C
A new stable hexanuclear silver(I) cluster features brightly blue phosphorescence at room temperature, which is integrated with yellow
phosphors (YAG : Ce3+) to white-light-emission film and demonstrates interesting mechanoresponsive luminescence.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins